US4774289A - Thermoplastic moulding compositions of polycarbonate and terpolymers - Google Patents
Thermoplastic moulding compositions of polycarbonate and terpolymers Download PDFInfo
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- US4774289A US4774289A US07/075,535 US7553587A US4774289A US 4774289 A US4774289 A US 4774289A US 7553587 A US7553587 A US 7553587A US 4774289 A US4774289 A US 4774289A
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- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 31
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 31
- 239000004415 thermoplastic moulding composition Substances 0.000 title claims abstract description 5
- 229920001897 terpolymer Polymers 0.000 title 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 16
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 15
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 27
- 229920001577 copolymer Polymers 0.000 claims description 20
- 238000000465 moulding Methods 0.000 claims description 11
- -1 C1 -C5 -alkylene radical Chemical class 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims 1
- 101150108015 STR6 gene Proteins 0.000 claims 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- 230000009477 glass transition Effects 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 229920000578 graft copolymer Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- KAIRTVANLJFYQS-UHFFFAOYSA-N 2-(3,5-dimethylheptyl)phenol Chemical compound CCC(C)CC(C)CCC1=CC=CC=C1O KAIRTVANLJFYQS-UHFFFAOYSA-N 0.000 description 1
- XBQRPFBBTWXIFI-UHFFFAOYSA-N 2-chloro-4-[2-(3-chloro-4-hydroxyphenyl)propan-2-yl]phenol Chemical compound C=1C=C(O)C(Cl)=CC=1C(C)(C)C1=CC=C(O)C(Cl)=C1 XBQRPFBBTWXIFI-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- CUAUDSWILJWDOD-UHFFFAOYSA-N 4-(3,5-dimethylheptyl)phenol Chemical compound CCC(C)CC(C)CCC1=CC=C(O)C=C1 CUAUDSWILJWDOD-UHFFFAOYSA-N 0.000 description 1
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 description 1
- NIRYBKWMEWFDPM-UHFFFAOYSA-N 4-[3-(4-hydroxyphenyl)-3-methylbutyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)CCC1=CC=C(O)C=C1 NIRYBKWMEWFDPM-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000005199 ultracentrifugation Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Definitions
- thermoplastic moulding compositions containing:
- thermoplastic copolymer of 30 to 40 parts by weight, preferably 34.5 parts by weight, of ⁇ -methylstyrene, 50 to 60 parts by weight, preferably 55.5 parts by weight, of methyl methacrylate and 5 to 15 parts by weight, preferably 10 parts by weight, of acrylonitrile.
- the moulding compositions, according to the invention, of (A) and (B) have only a single thermoplastic loss modulus maximum or exhibit only a single glass transition temperature, which corresponds to improved miscibility, in respect of polycarbonate/copolymer mixtures, in comparison with the prior art.
- the invention is based on the knowledge that a particular copolymer of ⁇ -methylstyrene, acrylonitrile and methyl methacrylate, it being possible for the amounts of the components to be varied only very slightly, has improved miscibility with polycarbonate and thus gives "compatible" polycarbonate/vinyl polymer mixtures.
- German Auslegeschrift No. 2,259,565 describes polycarbonate/graft polymer/copolymer mixtures in which the graft polymers have been prepared by polymerization of styrene, methyl methacrylate in combination with acrylonitrile and/or methyl methacrylate on a rubber and the copolymers thereof have been prepared from 95-50% of styrene, ⁇ -methylstyrene, methacrylate or mixtures thereof and 5-50% of acrylonitrile, methyl methacrylate or mixtures thereof. These compositions have an improved joint seam strength.
- German Offenlegungsschrift No. 1,810,993 describes polycarbonate/graft polymer/copolymer mixtures of the same type, the vinylaromatic compound used being predominantly ⁇ -methylstyrene. Such mixtures have a high heat distortion point but a poorer notched impact strength than analogous mixtures based on styrene.
- Thermoplastic aromatic polycarbonates (A) which are suitable according to the invention are those based on the diphenols of the formula (I) ##STR1## wherein A is a single bond, a C 1 -C 5 -alkylene radical, a C 2 -C 5 -alkylidene radical, a C 5 -C 6 -cycloalkylidene radical, --S-- or --SO 2 --;
- Hal is chlorine or bromine
- x 0, 1 or 2
- n 1 or 0,
- R denotes identical or different linear C 1 -C 20 -alkyl, branched C 3 -C 20 -alkyl or C 6 -C 20 -aryl radicals, preferably --CH 3 , and
- n is an integer from 5 to 100, preferably from 20 to 80.
- Polycarbonates (A) which are suitable according to the invention are homopolycarbonates of diphenols of the formula (I) and copolycarbonates of diphenols of the formula (I) and diphenols of the formula (Ia) in an amount by weight of 1 to 20% by weight, preferably 1.5 to 15% by weight and in particular 2 to 10% by weight, based on the total weight of the diphenols employed. Mixtures of a copolycarbonate based on diphenols (Ia) and (I) and another siloxane-free thermoplastic polycarbonate are also suitable, the amount of cocondensed diphenols (Ia) in the polycarbonate mixture being 1 to 20% by weight.
- diphenols of the formula (I) are known or can be prepared by known processes; polydiorganosiloxanes with hydroxy-aryloxy end groups according to formula (Ia) are likewise known (compare U.S. Pat. No. 3,419,634), or they can be prepared by known processes.
- polycarbonates (A) which are suitable according to the invention.
- the diphenols can be reacted with phosgene by the phase boundary process or in a homogeneous phase system (the so-called pyridine process), the molecular weight being established by an appropriate amount of chain stoppers (compare DE-OS (German Published Specification) No. 3,334,782).
- chain stoppers examples include phenol, p-chlorophenol, p-tert.-butylphenol and 2,4,6-tribromophenol, as well as long-chain alkylphenols, such as 4-(1,3-tetramethyl-butyl)-phenol (according to DE-OS (German Published Specification) No.
- the polycarbonates (A) which are suitable according to the invention have means weight-average molecular weights (Mw, measured by ultracentrifugation or scattered light measurement) of 10,000 to 200,000, preferably 20,000 to 80,000.
- Mw weight-average molecular weights
- diphenols of the formula (I) are hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis-(4-hydroxyphenyl)-propane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane and 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane.
- Preferred diphenols of the formula (I) are 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane and 1,1-bis-(4-hydroxyphenyl)-cyclohexane.
- Particularly suitable diphenols of the formula (Ia) are those in which R is methyl, ethyl, propyl, n-butyl, tert.-butyl and phenyl.
- n is an integer from 5 to 100, preferably from 20 to 80.
- the diphenols of the formula (Ia) can be prepared, for example, from the corresponding bis-chlorine compounds of the formula (II) ##STR4## wherein R and m have the meaning already given, and the diphenols of the formula (I) in accordance with U.S. Pat. No. 3,419,634, column 3, in combination with U.S. Pat. No. 3,182,662.
- the polycarbonates (A) which are suitable according to the invention can be branched, and in particular preferably by the incorporation of 0.05 to 2.0 mol %, based on the sum of the diphenols employed, of compounds which are trifunctional or more than trifunctional, for example those with three or more than three phenolic OH groups.
- Preferred polycarbonates are, in addition to the bisphenol A homopolycarbonate, the copolycarbonates of bisphenol A with up to 30% by weight, based on the total weight of diphenols, of 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane or the copolycarbonates of diphenols of the formula (I) with 1 to 20% by weight of diphenols of the formula (Ia), preferably of the formula (Ib), based on the total weight of the diphenols (I) and (Ia) or (I) and (Ib).
- the copolymers (B) are thermoplastic resinous polymers. They are known, and can be prepared by free radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. Their molecular weight Mw (weight-average, determined by light scattering or sedimentation) is 15,000 to 200,000, preferably ⁇ 100,000.
- Particularly preferred copolymers (B) are those of 34.5 parts by weight of ⁇ -methylstyrene, 55.5 parts by weight of methyl methacrylate and 10 parts by weight of acrylonitrile.
- the moulding compositions according to the invention can contain the customary amounts of other additives which are known for polycarbonate/graft polymer/copolymer moulding compositions, such as stabilizers, pigments, flow control agents, flameproofing agents, mould release agents and/or antistatics.
- additives which are known for polycarbonate/graft polymer/copolymer moulding compositions, such as stabilizers, pigments, flow control agents, flameproofing agents, mould release agents and/or antistatics.
- the present invention also relates to a process for the preparation of thermoplastic moulding compositions of components A, B and, if appropriate, known additives, such as stabilizers, pigments, flow control agents, flameproofing agents, mould release agents and antistatics, which is characterized in that components A and B and, if appropriate, additives are mixed and the mixture is then subjected to melt compounding or melt extrusion at temperatures of 200° C. to 330° C. in devices customary for this purpose, for example internal kneaders, extruders or twin-screw extruders.
- additives such as stabilizers, pigments, flow control agents, flameproofing agents, mould release agents and antistatics
- the components can be mixed in succession or simultaneously, at about 20° C. (room temperature) or at a higher temperature.
- moulding compositions of the present invention can be used to produce all types of mouldings, in particular by injection moulding.
- mouldings which can be produced are: machine housings (for example for domestic appliances, such as juice extractors, coffee machines and mixers), cover plates for buildings, motor vehicle components and components for electrical equipment (because of their good electrical properties).
- Mouldings can also be produced by deep-drawing from sheets and foils.
- the siloxane content in the polydiorganosiloxanepolycarbonate block copolymer that is to say the amount of dimethylsiloxy units in % by weight, based on the total weight of the block copolymer, can be determined gravimetrically and by nuclear magnetic resonance spectrometry.
- the degree of polymerization Pn determined by determination of the end group on the siloxane prepolymer (formula Ia) is stated as the average siloxane block length.
- Copolycarbonate based on bisphenol A with 10% by weight of tetrabromobisphenol A and a relative solution viscosity of 1.284, measured in CH 2 Cl 2 at 25° C. and at a concentration of 0.5 g/l; bromine content: about 5% by weight.
- Styrene/acrylonitrile copolymer with a styrene/acrylonitrile ratio of 72:28 and an L value of 60 prepared by bulk polymerization.
- Methyl methacrylate/acrylonitrile copolymer with a methyl methacrylate/acrylonitrile ratio of 70:30 and an L value of 77 prepared by emulsion polymerization.
- the L value is defined as the specific viscosity of a polymer solution in dimethylformamide (measured at 20° C.) at a concentration of 5 g/l divided by this concentration.
- the glass transition temperature was determined on cast films. These were prepared by dissolving the components in methylene chloride in the desired mixing ratio, casting the solution, evaporating off the solvent at room temperature and subsequently drying the films at 50°-70° C. under a slight vacuum.
- Injection moulded pieces produced at 260° C. were employed to determine the curve of the shear modulus (ASTM bar 1/8").
- the material employed for injection moulding was compounded on a 1.3 l internal kneader at a temperature of 200°-220° C.
- the glass transition temperature was determined by means of a differential calorimeter, DSC-2 (Perkin-Elmer). In this determination, each sample was heated up twice from +10° C. to 200° C. with a heating-up rate of 20 K/minute, under nitrogen as the inert gas. After the first heating up, the sample was cooled to 10° C. in the calorimeter at 320 K/minute. The measurement was made during the second heating up.
- DSC-2 differential calorimeter
- Table 1 shows that the mixture of the two components, polycarbonates and the copolymer according to the invention, has only a single glass transition point.
- Table 3 lists glass transition points for mixtures which contain, as the resin component, a copolymer with a composition which deviates from that of the resin according to the invention. Two glass transition points result in each case.
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Thermoplastic moulding compositions containing:
A. 1-99 parts by weight of an aromatic thermoplastic polycarbonate or several aromatic thermoplastic polycarbonates and
B. 1-99 parts by weight of a thermoplastic compolymer of 30-40 parts by weight of α-methylstyrene, 50-60 parts by weight of methyl methacrylate and 5-15 parts by weight of acrylonitrile.
Description
The present invention relates to thermoplastic moulding compositions containing:
A. 1-99 parts by weight, preferably 5-95 parts by weight, of an aromatic thermoplastic polycarbonate or several aromatic thermoplastic polycarbonates and
B. 1-99 parts by weight, preferably 5-95 parts by weight, of a thermoplastic copolymer of 30 to 40 parts by weight, preferably 34.5 parts by weight, of α-methylstyrene, 50 to 60 parts by weight, preferably 55.5 parts by weight, of methyl methacrylate and 5 to 15 parts by weight, preferably 10 parts by weight, of acrylonitrile.
The moulding compositions, according to the invention, of (A) and (B) have only a single thermoplastic loss modulus maximum or exhibit only a single glass transition temperature, which corresponds to improved miscibility, in respect of polycarbonate/copolymer mixtures, in comparison with the prior art.
Incompatibility due to the inadequate miscibility of the components is widespread in the preparation of polymer blends.
The invention is based on the knowledge that a particular copolymer of α-methylstyrene, acrylonitrile and methyl methacrylate, it being possible for the amounts of the components to be varied only very slightly, has improved miscibility with polycarbonate and thus gives "compatible" polycarbonate/vinyl polymer mixtures.
German Auslegeschrift No. 2,259,565 describes polycarbonate/graft polymer/copolymer mixtures in which the graft polymers have been prepared by polymerization of styrene, methyl methacrylate in combination with acrylonitrile and/or methyl methacrylate on a rubber and the copolymers thereof have been prepared from 95-50% of styrene, α-methylstyrene, methacrylate or mixtures thereof and 5-50% of acrylonitrile, methyl methacrylate or mixtures thereof. These compositions have an improved joint seam strength.
German Offenlegungsschrift No. 1,810,993 describes polycarbonate/graft polymer/copolymer mixtures of the same type, the vinylaromatic compound used being predominantly α-methylstyrene. Such mixtures have a high heat distortion point but a poorer notched impact strength than analogous mixtures based on styrene.
Mixtures of polycarbonate with graft polymers of mixtures of styrene, vinyltoluene, methyl methacrylate, acrylonitrile, methyl acrylate, hydroxyethyl acrylate or ethyl methacrylate on a diene rubber are described, for example, in Japanese Patent Application No. 56/131-657.
Thermoplastic aromatic polycarbonates (A) which are suitable according to the invention are those based on the diphenols of the formula (I) ##STR1## wherein A is a single bond, a C1 -C5 -alkylene radical, a C2 -C5 -alkylidene radical, a C5 -C6 -cycloalkylidene radical, --S-- or --SO2 --;
Hal is chlorine or bromine,
x is 0, 1 or 2 and
n is 1 or 0,
and, if appropriate, also of the formula (Ia) ##STR2## wherein A; Hal; x and n hve the meaning given in the case of formula (I), and
R denotes identical or different linear C1 -C20 -alkyl, branched C3 -C20 -alkyl or C6 -C20 -aryl radicals, preferably --CH3, and
m is an integer from 5 to 100, preferably from 20 to 80.
Polycarbonates (A) which are suitable according to the invention are homopolycarbonates of diphenols of the formula (I) and copolycarbonates of diphenols of the formula (I) and diphenols of the formula (Ia) in an amount by weight of 1 to 20% by weight, preferably 1.5 to 15% by weight and in particular 2 to 10% by weight, based on the total weight of the diphenols employed. Mixtures of a copolycarbonate based on diphenols (Ia) and (I) and another siloxane-free thermoplastic polycarbonate are also suitable, the amount of cocondensed diphenols (Ia) in the polycarbonate mixture being 1 to 20% by weight.
The diphenols of the formula (I) are known or can be prepared by known processes; polydiorganosiloxanes with hydroxy-aryloxy end groups according to formula (Ia) are likewise known (compare U.S. Pat. No. 3,419,634), or they can be prepared by known processes.
The preparation of polycarbonates (A) which are suitable according to the invention is known. For example, the diphenols can be reacted with phosgene by the phase boundary process or in a homogeneous phase system (the so-called pyridine process), the molecular weight being established by an appropriate amount of chain stoppers (compare DE-OS (German Published Specification) No. 3,334,782).
Examples of suitable chain stoppers are phenol, p-chlorophenol, p-tert.-butylphenol and 2,4,6-tribromophenol, as well as long-chain alkylphenols, such as 4-(1,3-tetramethyl-butyl)-phenol (according to DE-OS (German Published Specification) No. 2,842,005) and monoalkylphenols and dialkylphenols with a total of 8 to 20 C atoms in the alkyl substituents (according to German Patent Application P-350647.2), such as p-nonylphenol, 3,5-di-tert.-butylphenol, p-tert.-octylphenol, p-dodecylphenol, 2-(3,5-dimethyl-heptyl)-phenol and 4-(3,5-dimethylheptyl)-phenol.
The polycarbonates (A) which are suitable according to the invention have means weight-average molecular weights (Mw, measured by ultracentrifugation or scattered light measurement) of 10,000 to 200,000, preferably 20,000 to 80,000.
Examples of suitable diphenols of the formula (I) are hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis-(4-hydroxyphenyl)-propane, 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-cyclohexane, 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane and 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane.
Preferred diphenols of the formula (I) are 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane and 1,1-bis-(4-hydroxyphenyl)-cyclohexane.
Particularly suitable diphenols of the formula (Ia) are those in which R is methyl, ethyl, propyl, n-butyl, tert.-butyl and phenyl.
Preferred diphenols of the formula (Ia) corresponding to the formula (Ib) ##STR3## wherein the two radicals R are identical and have the abovementioned meaning, and preferably represent methyl and the like or phenyl, and
m is an integer from 5 to 100, preferably from 20 to 80.
The diphenols of the formula (Ia) can be prepared, for example, from the corresponding bis-chlorine compounds of the formula (II) ##STR4## wherein R and m have the meaning already given, and the diphenols of the formula (I) in accordance with U.S. Pat. No. 3,419,634, column 3, in combination with U.S. Pat. No. 3,182,662.
The polycarbonates (A) which are suitable according to the invention can be branched, and in particular preferably by the incorporation of 0.05 to 2.0 mol %, based on the sum of the diphenols employed, of compounds which are trifunctional or more than trifunctional, for example those with three or more than three phenolic OH groups.
Preferred polycarbonates are, in addition to the bisphenol A homopolycarbonate, the copolycarbonates of bisphenol A with up to 30% by weight, based on the total weight of diphenols, of 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane or the copolycarbonates of diphenols of the formula (I) with 1 to 20% by weight of diphenols of the formula (Ia), preferably of the formula (Ib), based on the total weight of the diphenols (I) and (Ia) or (I) and (Ib).
The copolymers (B) are thermoplastic resinous polymers. They are known, and can be prepared by free radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization. Their molecular weight Mw (weight-average, determined by light scattering or sedimentation) is 15,000 to 200,000, preferably <100,000.
Particularly preferred copolymers (B) are those of 34.5 parts by weight of α-methylstyrene, 55.5 parts by weight of methyl methacrylate and 10 parts by weight of acrylonitrile.
The moulding compositions according to the invention can contain the customary amounts of other additives which are known for polycarbonate/graft polymer/copolymer moulding compositions, such as stabilizers, pigments, flow control agents, flameproofing agents, mould release agents and/or antistatics.
The present invention also relates to a process for the preparation of thermoplastic moulding compositions of components A, B and, if appropriate, known additives, such as stabilizers, pigments, flow control agents, flameproofing agents, mould release agents and antistatics, which is characterized in that components A and B and, if appropriate, additives are mixed and the mixture is then subjected to melt compounding or melt extrusion at temperatures of 200° C. to 330° C. in devices customary for this purpose, for example internal kneaders, extruders or twin-screw extruders.
The components can be mixed in succession or simultaneously, at about 20° C. (room temperature) or at a higher temperature.
The moulding compositions of the present invention can be used to produce all types of mouldings, in particular by injection moulding. Examples of mouldings which can be produced are: machine housings (for example for domestic appliances, such as juice extractors, coffee machines and mixers), cover plates for buildings, motor vehicle components and components for electrical equipment (because of their good electrical properties).
Mouldings can also be produced by deep-drawing from sheets and foils.
The siloxane content in the polydiorganosiloxanepolycarbonate block copolymer, that is to say the amount of dimethylsiloxy units in % by weight, based on the total weight of the block copolymer, can be determined gravimetrically and by nuclear magnetic resonance spectrometry. The degree of polymerization Pn determined by determination of the end group on the siloxane prepolymer (formula Ia) is stated as the average siloxane block length.
Polycondensates and polymers employed:
Polycarbonate of 2,2-bis-(4-hydroxyphenyl)propane (bisphenol A) with a relative solution viscosity of 1.26-1.28, measured in methylene chloride at 25° C. and at a concentration of 0.5% by weight.
Polycarbonate of 2,2-bis-(4-hydroxyphenyl)propane (bisphenol A) with a relative solution viscosity of 1.30-1.32, measured in methylene chloride at 25° C. and at a concentration of 0.5%.
Copolycarbonate based on bisphenol A with 10% by weight of tetrabromobisphenol A and a relative solution viscosity of 1.284, measured in CH2 Cl2 at 25° C. and at a concentration of 0.5 g/l; bromine content: about 5% by weight.
Copolycarbonate of basis of bisphenol A and 5% by weight of polydimethylsiloxane of block length (Pn) 40, with a relative solution viscosity of 1.31, measured in CH2 Cl2 at 25° C. and at a concentration of 0.5 g/100 ml.
A thermoplastic copolymer of 34.5% by weight of α-methylstyrene, 55.5% by weight of methyl methacrylate and 10% by weight of acrylonitrile, with an L value of 58, prepared by emulsion polymerization.
Copolymer according to B 1 with an L value of 40.
Copolymer according to B 1 with an L value of 42.
Copolymer according to B 1 with an L value of 41.
Copolymer according to B 1 with an L value of 48.
Copolymer according to B 1 with an L value of 49.
Styrene/acrylonitrile copolymer with a styrene/acrylonitrile ratio of 72:28 and an L value of 60, prepared by bulk polymerization.
Methyl methacrylate/acrylonitrile copolymer with a methyl methacrylate/acrylonitrile ratio of 70:30 and an L value of 77, prepared by emulsion polymerization.
A copolymer of 50% by weight of α-methylstyrene, 35.5% by weight of methyl methacrylate, 14.5% by weight of acrylonitrile, with an L value of 43, prepared by emulsion polymerization.
A copolymer of 24.5% by weight of α-methylstyrene, 64% by weight of methyl methacrylate and 11.5% by weight of acrylonitrile, with an L value of 36, prepared by emulsion polymerization.
A copolymer of 14.5% by weight of α-methylstyrene, 72.5% by weight of methyl methacrylate and 13% by weight of acrylonitrile, with an L value of 36, prepared by emulsion polymerization.
The L value is defined as the specific viscosity of a polymer solution in dimethylformamide (measured at 20° C.) at a concentration of 5 g/l divided by this concentration.
The glass transition temperature was determined on cast films. These were prepared by dissolving the components in methylene chloride in the desired mixing ratio, casting the solution, evaporating off the solvent at room temperature and subsequently drying the films at 50°-70° C. under a slight vacuum.
Injection moulded pieces produced at 260° C. were employed to determine the curve of the shear modulus (ASTM bar 1/8").
The material employed for injection moulding was compounded on a 1.3 l internal kneader at a temperature of 200°-220° C.
The glass transition temperature was determined by means of a differential calorimeter, DSC-2 (Perkin-Elmer). In this determination, each sample was heated up twice from +10° C. to 200° C. with a heating-up rate of 20 K/minute, under nitrogen as the inert gas. After the first heating up, the sample was cooled to 10° C. in the calorimeter at 320 K/minute. The measurement was made during the second heating up.
In order to determine the glass transition point by means of shear modulus measurement, a Rheometrie RDS 7700 Rheometric Dynamie spectrometer (measurement frequency 1 Hz) was used. Measurement was performed on the injection moulded pieces in their initial state.
The polycarbonate/copolymer mixtures investigated and the associated measurement results are given in the following tables:
TABLE 1 ______________________________________ A 1 B 1 B 2 B 3 Glass transition point (parts by weight) (DSC) (°C.) ______________________________________ 100 -- 146 90 10 142 70 30 124 50 50 122 30 70 120 10 90 114 0 100 112 90 10 142 50 50 123 30 70 118 10 90 115 20 80 117 30 70 120 40 60 124 70 30 130 ______________________________________
TABLE 2
______________________________________
Glass tran-
sition point
(Shear
A 1 A 2 A 3 A 4 B 4 B 5 B 6 (DSC) mod-
(parts by weight) (°C.)
ulus)
______________________________________
30 70 126
30 70 126
30 70 126
30 70 123
30 70 121
20 80 121
40 60 124
______________________________________
TABLE 3 ______________________________________ A 1 B 7 B 8 B 9 B 10 B 11 Glass transition point (parts by weight) (DSC) (°C.) ______________________________________ 10 90 106/138 30 70 107/136 50 50 109/140 70 30 107/138 90 10 112/145 30 70 90/129 70 30 91/139 0 100 87/-- 30 70 112/139 -- 100 116/-- 30 70 112/130 70 30 117/138 0 100 105/-- 30 70 104/128 70 30 108/136 -- 100 99/-- ______________________________________
Table 1 shows that the mixture of the two components, polycarbonates and the copolymer according to the invention, has only a single glass transition point.
From Table 2, it can be seen that the better miscibility is independent of the type of polycarbonate employed and the method of preparing the mixture.
Table 3 lists glass transition points for mixtures which contain, as the resin component, a copolymer with a composition which deviates from that of the resin according to the invention. Two glass transition points result in each case.
Claims (5)
1. A thermoplastic moulding composition containing
(A) 1 to 99 parts by weight of an aromatic thermoplastic polycarbonate or several aromatic thermoplastic polycarbonates and
(B) 1 to 99 parts by weight of a thermoplastic copolymer of 30 to 40 parts by weight of α-methylstyrene, 50 to 60 parts by weight of methyl methacrylate and 5 to 15 parts by weight of acrylonitrile.
2. A moulding composition according to claim 1, containing 5 to 95 parts by weight of the polycarbonate(s) of component (A) and 5 to 95 parts by weight of the copolymer of component (B).
3. A moulding composition according to claim 1, in which the copolymer of component (B) consists of 34.5 parts by weight of α-methylstyrene units, 55.5 parts by weight of methyl methacrylate units and 10 parts by weight of acrylonitrile units.
4. A moulding composition according to claim 1, in which the aromatic thermoplastic polycarbonate(s) of component (A) comprise a polycarbonate which contains 1 to 20% by weight, based on the total weight of diphenol employed, of incorporated diphenols of the general formula ##STR5## in which A denotes a single bond, a C1 -C5 -alkylene radical, a C2 -C5 -alkylidene radical, a C5 -C6 -cyclo-alkylidene radical, --S-- or --SO2 --;
Hal denotes a chlorine or bromine atom,
x is 0, 1 or 2,
n is 1 or 0.
5. A moulding composition according to claim 1, in which the aromatic thermoplastic polycarbonate(s) of component (A) comprise a copolycarbonate which contains 1 to 20% by weight, based on the total weight of the diphenols employed, of incorporated diphenols of formula (I), as defined in claim 4, and diphenols of the general formula ##STR6## wherein A is a single bond, a C1 -C5 -alkylene radical, a C2 -C5 -alkylidene radical, a C5 -C6 -cycloalkylidene radical, --S-- or --SO2 --;
Hal is chlorine or bromine,
x is 0, 1 or 2,
n is 1 or 0,
the radicals R are identical or different and denoe linear C1 -C20 -alkyl, branched C3 -C20 -alkyl or C6 -C20 -aryl radicals, and m is an integer from 5 to 100.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19863626258 DE3626258A1 (en) | 1986-08-02 | 1986-08-02 | THERMOPLASTIC MOLDS FROM POLYCARBONATE AND TERPOLYMERISATEN |
| DE3626258 | 1986-08-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4774289A true US4774289A (en) | 1988-09-27 |
Family
ID=6306592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/075,535 Expired - Fee Related US4774289A (en) | 1986-08-02 | 1987-07-20 | Thermoplastic moulding compositions of polycarbonate and terpolymers |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4774289A (en) |
| EP (1) | EP0255641B1 (en) |
| JP (1) | JPS6341563A (en) |
| DE (2) | DE3626258A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5241005A (en) * | 1990-12-28 | 1993-08-31 | Nippon Steel Chemical Co., Ltd. | Heat-resistant resin compositions with a pearly luster |
| US5352500A (en) * | 1988-02-08 | 1994-10-04 | Rohm And Haas Company | Thermoplastic polymer compositions containing melt-rheology modifiers |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3811054A1 (en) * | 1988-03-31 | 1989-10-12 | Basf Ag | Heat-distortion-resistant, thermoplastic moulding composition containing a terpolymer |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4579909A (en) * | 1984-12-18 | 1986-04-01 | General Electric Company | Ternary combination of acrylate-styrene-acrylonitrile terpolymer, poly methyl methacrylate and polycarbonate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3514185A1 (en) * | 1985-04-19 | 1986-10-23 | Bayer Ag, 5090 Leverkusen | THERMOPLASTIC MOLDS OF POLYCARBONATE, GRAFT POLYMERISATEN AND COPOLYMERISATEN |
-
1986
- 1986-08-02 DE DE19863626258 patent/DE3626258A1/en not_active Withdrawn
-
1987
- 1987-07-20 EP EP87110464A patent/EP0255641B1/en not_active Expired - Lifetime
- 1987-07-20 US US07/075,535 patent/US4774289A/en not_active Expired - Fee Related
- 1987-07-20 DE DE8787110464T patent/DE3774026D1/en not_active Expired - Lifetime
- 1987-07-29 JP JP62187851A patent/JPS6341563A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4579909A (en) * | 1984-12-18 | 1986-04-01 | General Electric Company | Ternary combination of acrylate-styrene-acrylonitrile terpolymer, poly methyl methacrylate and polycarbonate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5352500A (en) * | 1988-02-08 | 1994-10-04 | Rohm And Haas Company | Thermoplastic polymer compositions containing melt-rheology modifiers |
| US5241005A (en) * | 1990-12-28 | 1993-08-31 | Nippon Steel Chemical Co., Ltd. | Heat-resistant resin compositions with a pearly luster |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0255641B1 (en) | 1991-10-23 |
| DE3774026D1 (en) | 1991-11-28 |
| JPS6341563A (en) | 1988-02-22 |
| DE3626258A1 (en) | 1988-02-11 |
| EP0255641A2 (en) | 1988-02-10 |
| EP0255641A3 (en) | 1988-07-06 |
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